Exxonmobil Chemical Patents Inc.

John Stephen Godsmark

Stephen Harold Brown

Raphael Frans Caers

Hubertus Joseph Beckers

Georges M K Mathys

Georges Marie Karel Mathys

John Richard Shutt

Eddy Theophile Van Driessche

Luc R M Martens

Marcel Johannes Janssen

Paul Hamilton

Stephen Wayne Beadle

Yeo-Meng Lim

Charles Morris Yarbrough

Jose M Vargas

Roger Eijkhoudt

J Richard Shutt

Jon Edmond Randoph Stanat

Georges Marie K Mathys

Jihad Mohammed Dakka

Keith Holroyd Kuechler

Steven E Silverberg

Luc Roger Martens

Georges Marie Mathys

Luc Roger Marc Martens

An Verberckmoes

Hans K T Goris

Marc P H Puttemans

Marc P Puttemans

Raphael Frans Ivo Caers

Eddy Theophyle Andrea Van Driessche

Hans Karel Theresia Goris

Luc Rm Martens

Mark R Welford

Robert L Wolf

David E Heather

George Marie Karel Mathys

Georges Maria Karel Mathys

Eddy Theophile Andrea Van Driessche

John Richard Schutt

Stephen H Brown

Charles M Yarbrough

Hubertus J Beckers

Marc PH Puttemans

Hans KT Goris

RFI Caers

Stephen Brown

Luc RM Martens

A process for the oligomerization of olefins includes treating, e.g., water washing, an olefin-containing hydrocarbon stream to lower the concentration of an organic nitrogen-containing Lewis base contained therein until the treated hydrocarbon stream is substantially free of the Lewis base; and subsequently contacting the treated hydrocarbon stream with a molecular sieve catalyst to produce a product including at least one oligomer.

Lowering nitrogen-containing Lewis bases in molecular sieve oligomerisation

Deactivation of a zeolite catalyst during its use to catalyse the oligomerisation of olefins, is often believed to be a result of the formation of high boiling polymers as by-products. These by-products can remain on the catalyst and undergo further conversion to higher molecular weight polymers, which resemble heavy tars and in some cases even have the appearance of coke-like material. These materials can coat the catalyst particles and plug pores in the catalyst, thereby causing catalyst deactivation. The invention relates to an improved method for regenerating such a catalyst.

Regeneration of oligomerisation catalysts and their use

The startup of a tubular reactor containing fresh or regenerated molecular sieve catalyst and cooled by steam generation on the shell side, as part of an olefin oligomerization process, is improved by, during the startup phase of the reactor, controlling the pressure on the shell side of the reactor at maximum 10 barg. The startup may be further improved by controlling the inlet temperature of the hydrocarbon startup stream to the reactor, by controlling the flow of reactant olefins to the reactor, or by controlling the nature and/or concentration of the olefins in the reactor feed.

Oligomerisation process

The conversion and run length for oligomerization of olefins over a molecular sieve catalyst in a tubular reactor is improved by controlling the peak temperature to not exceed 50 degrees C. above the temperature of the temperature control fluid exiting the shell side outlet of the reactor. A tubular reactor containing molecular sieve catalyst is provided with a multipoint thermocouple in at least one tube, and optionally with a bottom design adapted for fast unloading of the molecular sieve catalyst from the tubular reactor.

Oligomerisation of olefins with zeolite catalyst

In a process for oligomerizing an olefinic hydrocarbon feedstock comprising at least 65 wt % olefins and/or sulfur-containing molecules, the feedstock is contacted under oligomerization conditions with (a) a first unidimensional 10-ring molecular sieve catalyst and (b) a second multidimensional crystalline molecular sieve catalyst. The first and second catalysts may be contained in separate reactors or as separate beds in a single reactor.

Olefin oligomerization process

Olefin feeds with high olefin content and/or containing a substance that generates water when contacting the catalyst, are oligomerised over solid phosphoric acid catalyst in tubular reactors by introducing the olefin feed into the reactor and maintaining the reacting mixture under conditions whereby the peak temperature is controlled to be below 265&#xb0; C. and preferably a single liquid or dense phase is maintained and the average temperature throughout the reactor is maintained in the range 190&#xb0; C. to 260&#xb0; C.

Oligomerisation of olefins

The invention relates to series reactor beds containing different oligomerization catalysts and having independent temperature control, and processes for the oligomerization of light olefins to heavier olefins using such series reactor beds.

Series catalyst beds

A hydrocarbon composition that comprises species of at least 3 different carbon numbers, at least about 95 wt % non-normal hydrocarbons, no greater than 1000 wppm aromatics, no greater than 10 wt % naphthenes, and also has a certain boiling point range; and a process for making the hydrocarbon composition.

Olefin oligomerization and compositions therefrom

In the oligomerization of olefins in a tubular reactor employing a molecular sieve catalyst, the temperature of the reaction is monitored and the space velocity of the olefin feed to the reactor is reduced as the temperature increases. This has been found to increase catalyst life and lead to extended production runs. Further extensions of the production run are achieved by improving reactor operating stability as the end of the production run approaches.

Nitrogen-containing Lewis bases act as poisons for molecular sieve catalysts used in oligomerisation reactions. A lowering of their presence in the feed prior to the contacting thereof with the molecular sieve brings a significant extension of catalyst life. Excessive elimination of these poisons may be disadvantageous. Lowering the levels of these catalyst poisons to more manageable concentrations is therefore preferred.

Water reacts on molecular sieve catalysts used in oligomerization reactions and forms oxygenated compounds, in particular organic acids that may cause corrosion problems downstream of the reactor, in particular in distillation tower overhead systems and downstream thereof. A lowering of the presence of water in the feed prior to contacting thereof with the molecular sieve brings a significant reduction in corrosion downstream. At the same time, it has a significant beneficial effect on catalyst activity and brings a significant extension of catalyst life. Lowering water in the feed is particularly effective when organic nitrogen-containing Lewis bases are present in the feed, even at low levels.

Low corrosion in zeolite oligomerisation

In a process for oligomerizing an olefinic hydrocarbon feedstock, the feedstock is contacted under oligomerization conditions with (a) a first crystalline molecular sieve catalyst and (b) a second catalyst comprising a solid phosphoric acid. The first and second catalysts may be contained in separate reactors or as separate beds in a single reactor.

Propylene streams obtained by the conversion of oxygenates to olefins are used as feeds for hydroformylation. The streams may contain measurable amounts of dimethyl ether without adversely impacting the hydroformylation.

Propylene hydroformylation

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Grez Doiceau, Belgium

John Stephen Godsmark